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Abstract:

The present invention relates to a photoreactive polymer that comprises a
multi-cyclic compound in a main chain, and a polymerization method
thereof. Since the photoreactive polymer according to the present
invention comprises a multi-cyclic compound having a high glass
transition temperature as a main chain, the thermal stability is
excellent, and since the mobility of the main chain is relatively high as
compared to that of an additional polymer, a photoreactive group can be
freely moved in the main chain of the polymer. Accordingly, it is
possible to overcome a slow photoreactive rate that is considered a
disadvantage of a polymer material used to prepare an alignment film for
known liquid crystal display devices.

Claims:

1. A multi-cyclic compound that is represented by the following Formula
1: ##STR00016## wherein P is an integer in the range of 0 to 4, at
least one of R1, R2, R3, and R4 is a radical that is
selected from the group consisting of the following Formula 1a, the
remains of R1, R2, R3, and R4 are each independently
selected from the group consisting of hydrogen; halogen; substituted or
unsubstituted C1-C20 alkyl; substituted or unsubstituted C2-C20 alkenyl;
substituted or unsubstituted saturated or unsaturated C5-C12 cycloalkyl;
substituted or unsubstituted C6-C40 aryl; substituted or unsubstituted
C7-C15 aralkyl; substituted or unsubstituted C2-C20 alkynyl; and a
non-hydrocarbonaceous polar group that comprises one or more elements
selected from the group consisting of oxygen, nitrogen, phosphorus,
sulfur, silicon, and boron, R1 and R2 or R3 and R4
may be bonded to each other to form a C1-C10 alkylidene group, or R1
or R2 may be bonded to any one of R3 and R4 to form a
saturated or unsaturated C4-C12 ring or an aromatic ring having 6 to 24
carbon atoms, ##STR00017## wherein A is substituted or unsubstituted
C1-C20 alkylene, carbonyl, carboxy, substituted or unsubstituted C6-40
arylene, or a simple bond; B is oxygen, sulfur, --NH--, or a simple bond;
R9 is a simple bond, substituted or unsubstituted C1-C20 alkylene;
substituted or unsubstituted C2-C20 alkenylene; substituted or
unsubstituted C5-C12 cycloalkylene; substituted or unsubstituted C6-C40
arylene; substituted or unsubstituted C7-C15 aralkylene; or substituted
or unsubstituted C2-C20 alkynylene; C is C6-C40 aryl; or C6-C40 hetero
aryl that comprises Group 14, 15 or 16 hetero elements, and the aryl or
hetero aryl is substituted with substituted or unsubstituted C1-C20
alkoxy or substituted or unsubstituted C6-C30 aryloxy; the
non-hydrocarbonaceous polar group is --OR6, --OC(O)OR6,
--R5OR6, --R5OC(O)OR6, --C(O)OR6,
--R5C(O)OR6, --C(O)R6, --R5C(O)R6,
--OC(O)R6, --R5OC(O)R6, --(R5O)p--OR6 (p is
an integer in the range of 1 to 10), --(OR5)p--OR6 (p is
an integer in the range of 1 to 10), --C(O)--O--C(O)R6,
--R5C(O)--O--C(O)R6, --SR6, --R5SR6,
--SSR6, --R5SSR6, --S(═O)R6,
--R5S(═O)R6, --R5C(═S)R6,
--R6C(═S)SR6, --R5SO3R6, --SO3R6,
--R5N═C═S, --N═C═S, --NCO, --R5--NCO, --CN,
--R5CN, --NNC(═S)R6, --R5NNC(═S)R6,
--NO2, --R5NO2, ##STR00018## ##STR00019## ##STR00020##
in the non-hydrocarbonaceous polar group, R5 may be selected from
the group consisting of substituted or unsubstituted C1-C20 alkylene;
substituted or unsubstituted C2-C20 alkenylene; substituted or
unsubstituted saturated or unsaturated (5-C12 cycloalkylene; substituted
or unsubstituted C6-C40 arylene; substituted or unsubstituted C7-C15
aralkylene; and substituted or unsubstituted C2-C20 alkynylene, and
R6, R7 and R8 may be selected from the group consisting of
each independently hydrogen; halogen; substituted or unsubstituted C1-C20
alkyl; substituted or unsubstituted C2-C20 alkenyl; substituted or
unsubstituted saturated or unsaturated C5-C12 cycloalkyl; substituted or
unsubstituted C6-C40 aryl; substituted or unsubstituted C7-C15 aralkyl;
and substituted or unsubstituted C2-C20 alkynyl.

2. The multi-cyclic compound as set forth in claim 1, wherein in Formula
1a, C is any one selected from the group consisting of compounds
represented by the following Formulae: ##STR00021## wherein at least
one of R'10, R'11, R'12, R'13, R'14, R'15,
R'16, R'17, and R'18 is necessarily substituted or
unsubstituted C1-C20 alkoxy or substituted or unsubstituted C6-C30
aryloxy, and the remains are each independently hydrogen, substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy,
substituted or unsubstituted C6-C30 aryloxy, or substituted or
unsubstituted C6-C40 aryl.

3. A photoreactive polymer comprising the compound of claim 1 as a
monomer in a main chain and a repeating unit that is represented by the
following Formula 3: ##STR00022## wherein n is in the range of 50 to
5,000, and P, R1, R2, R3, and R4 are the same as those defined in Formula
1.

4. The photoreactive polymer as set forth in claim 3, wherein in Formula
1a, C is any one selected from the group consisting of compounds
represented by the following Formulae: ##STR00023## wherein at least
one of R'10, R'11, R'12, R'13, R'14, R'15,
R'16, R'17, and R'18 is necessarily substituted or
unsubstituted C1-C20 alkoxy or substituted or unsubstituted C6-C30
aryloxy, and the remains are each independently hydrogen, substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy,
substituted or unsubstituted C6-C30 aryloxy, or substituted or
unsubstituted C6-C40 aryl.

5. The photoreactive polymer as set forth in claim 3, further comprising
one or more of the multi-cyclic compounds that are represented by the
following Formula 4 as a monomer: ##STR00024## wherein P' is an integer
in the range of 0 to 4, R'1, R'2, R'3, and R'4 are
each independently selected from the group consisting of hydrogen;
halogen; substituted or unsubstituted C1-C20 alkyl, substituted or
unsubstituted C2-C20 alkenyl; substituted or unsubstituted C5-C12
cycloalkyl; substituted or unsubstituted C6-C40 aryl; substituted or
unsubstituted C7-C15 aralkyl; substituted or unsubstituted C2-C20
alkynyl; and a non-hydrocarbonaceous polar group that comprises one or
more elements selected from the group consisting of oxygen, nitrogen,
phosphorus, sulfur, silicon, and boron, if R'1, R'2, R'3,
and R'4 are not hydrogen, halogen, or a polar functional group,
R'1 and R'2, or R'3 and R'4 may be bonded to each
other to form a C1-C10 alkylidene group, or R'1 or R'2 may be
bonded to any one of R'3 and R'4 to form a saturated or
unsaturated C4-C12 ring or an aromatic ring having 6 to 24 carbon atoms,
the non-hydrocarbonaceous polar group is OR6, --OC(O)OR6,
--R5OR6, --R5OC(O)OR6, --C(O)OR6,
--R5C(O)OR6, --C(O)R6, --R5C(O)R6,
--OC(O)R6, --R5OC(O)R6, --(R5O)p--OR6 (p is
an integer in the range of 1 to 10), --(OR5)p--OR6 (p is
an integer in the range of 1 to 10), --C(O)--O--C(O)R6,
--R5C(O)--O--C(O)R6, --SR6, --R5SR6,
--SSR6, --R5SSR6, --S(═O)R6,
--R5S(═O)R6, --R5C(═S)R6,
--R6C(═S)SR6, --R5SO3R6, --SO3R6,
--R5N═C°S, --N═C═S, --NCO, --R5--NCO, --CN,
--R5CN, --NNC(═S)R6, --R5NNC(═S)R6,
--NO2, --R5NO2, ##STR00025## ##STR00026## ##STR00027##
R5 of each of the functional groups is substituted or unsubstituted
C1-C20 alkylene; substituted or unsubstituted C2-C20 alkenylene;
substituted or unsubstituted C5-C12 cycloalkylene; substituted or
unsubstituted C6-C40 arylene; substituted or unsubstituted C7-C15
aralkylene; or substituted or unsubstituted C2-C20 alkynylene, and
R6, R7 and R8 are each hydrogen; halogen; substituted or
unsubstituted C1-C20 alkyl; substituted or unsubstituted C2-C20 alkenyl;
substituted or unsubstituted C5-C12 cycloalkyl; substituted or
unsubstituted C6-C40 aryl; substituted or unsubstituted C7-C15 aralkyl;
or substituted or unsubstituted C2-C20 alkynyl.

6. A method of preparing a photoreactive polymer, the method comprising:
polymerizing the multi-cyclic compound of claim 1 in the presence of a
catalyst mixture that comprises a procatalyst including Group 4, Group 6,
and Group 8 transition metals, a occatalyst that provides a Lewis base
capable of being weakly coordinate bonded to the metal of the
procatalyst, and selectively activators including neutral Group 15 and
Group 16 elements that may improve the activity of the procatalyst metal,
at a temperature in the range of 10 to 200.degree. C. while linear
alkene, which is capable of controlling a size of a molecular weight, is
added; and adding a catalyst that comprises Group 4 or Group 8 to Group
10 transition metals to add hydrogen to a double bond remaining on a main
chain at a temperature in the range of 10 to 250.degree. C.

7. The method of preparing a photoreactive polymer as set forth in claim
6, wherein the catalyst mixture comprises 1 to 100,000 mole of the
cocatalyst, and selectively 1 to 100 mole of the activators that
comprises neutral Group 15 and Group 16 elements improving the activity
of the procatalyst metal based on 1 mole of the procatalyst.

8. The method of preparing a photoreactive polymer as set forth in claim
6, wherein the procatalyst is selected from the group consisting of
TiCl4, WCl6, MoCl5, RuCl3, and ZrCl.sub.4.

9. The method of preparing a photoreactive polymer as set forth in claim
6, wherein the cocatalyst is selected from the group consisting of
substituents comprising borane, borate, alkylaluminum, alkyl aluminoxane,
alkylaluminum halide, aluminum halide, lithium, magnesium, germanium,
lead, zinc; tin, and silicon.

10. The method of preparing a photoreactive polymer as set forth in claim
6, wherein the catalyst mixture comprises linear alkene, which is capable
of controlling the size of the molecular weight, in an amount of 1 to 100
mol % based on the monomer that is the multi-cyclic compound.

11. The method of preparing a photoreactive polymer as set forth in claim
6, wherein the catalyst that comprises the Group 4, Group 8, Group 9, or
Group 10 transition metals used during the hydrogenation reaction is
present in a homogeneous form that can be immediately mixed with a
solvent or a substance in which the metal catalyst complex compound is
carried in a fine supporting material, and the fine supporting material
is silica, titania, silica/chromia, silica/chromia/titania,
silica/alumina, aluminum phosphate gel, silanized silica, silica
hydrogel, montmorilonite clay, or zeolite.

12. A photoreactive polymer that is represented by the following Formula
5: ##STR00028## wherein n is the degree of polymerization in the range
of 50 to 5000, the content of the repeating unit of cycloolefin that is
represented by x is in the range of 0.1 to 99.9 mol %, the content of the
repeating unit of linear olefin that is represented by y is in the range
of 0.1 to 99.9 mol %, the content of the repeating unit of cycloolefin
that is represented by z is in the range of 0.1 to 99.9 mol %, the order
of the repeatition of noncycloolefin and cycloolefin is random, P,
R1, R2, R3, and R4 are the same as those defined in
Formula 1, Ra is a hydrogen atom or a C1-C20 hydrocarbon group, and P',
R1', R2', R3', and R4' are the same as those defined
in Formula 4.

13. The photoreactive polymer as set forth in claim 12, wherein in
Formula 1a, C is any one selected from the group consisting of compounds
represented by the following Formulae: ##STR00029## wherein at least
one of R'10, R'11, R'12, R'13, R'14, R'15,
R'16, R'17, and R'18 is necessarily substituted or
unsubstituted C1-C20 alkoxy or substituted or unsubstituted C6-C30
aryloxy, and the remains are each independently selected from the group
consisting of hydrogen, substituted or unsubstituted C1-C20 alkyl,
substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted
C6-C30 aryloxy, and substituted or unsubstituted C6-C40 aryl.

14. A method of preparing the photoreactive polymer of claim 12, the
method comprising: polymerizing a noncycloolefin monomer and a
cycloolefin monomer that comprises a photoactive functional group in the
presence of a catalyst mixture that consists of a procatalyst comprising
a metallocene catalyst and a cocatalyst comprising aluminoxane at a
temperature in the range of 10 to 200.degree. C. under polymerization
pressure in the range of 1 to 69 bar.

15. The method of preparing the photoreactive polymer as set forth in
claim 14, wherein the catalyst mixture comprises 10.sup.-4 to 10.sup.-2
mole of the procatalyst based on 1 mole of the occatalyst.

16. The method of preparing the photoreactive polymer as set forth in
claim 14, wherein the procatalyst is selected from the group consisting
of rac-ethylene-bis-(1-indenyl)-zirconiumdichloride,
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconiumdichloride,
rac-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride,
phenylmethyl-(9-fluorenyl)-cyclopentadienyl zirconium dichloride,
rac-dimethylgermyl-bis-(1-indenyl)-zirconium dichloride,
rac-phenyl-methylsilyl-bis-(1-indenyl)-zirconium dichloride, and
rac-phenylvinylsilyl-bis-(1-indenyl)-zirconium dichloride.

17. The method of preparing the photoreactive polymer as set forth in
claim 14, wherein the aluminoxane is selected from the group consisting
of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl
aluminoxane.

18. The method of preparing the photoreactive polymer as set forth in
claim 14, wherein the transition metal compound (catalyst and occatalyst)
is activated in a solution for 15 to 60 minutes and the temperature is
previously set to a range of 15 to 70.degree. C.

Description:

[0001] This application is a divisional application of U.S. patent
application Ser. No. 12/450,314, filed on Sep. 21, 2009, which is a
national stage application of International Application No.
PCT/KR2008/001608, filed on Mar. 21, 2008, which claims priority to
Korean Patent Application Nos. 10-2007-0028114, filed on Mar. 22, 2007,
and 10-2007-0028104, filed on Mar. 22, 2007, all of which are hereby
incorporated herein by reference for all purposes in their entirety.

TECHNICAL FIELD

[0002] The present invention relates to a photoreactive polymer, and more
particularly to a photoreactive polymer that has an alignment property
due to a photoreaction and includes a multi-cyclic compound in a main
chain, thus having the excellent thermal stability and allowing the
photoreaction to be rapid.

BACKGROUND ART

[0003] In recent years, a liquid crystal display that has a light weight
and consumes a small amount of electric power has been used as a most
competitive display that can be used instead of a cathode ray tube. In
particular, since a thin film transistor liquid crystal display (TFT-LCD)
that is driven by using a thin film transistor independently drives each
of pixels, a response speed of the liquid crystal is very high, thus, a
high-quality dynamic image can be realized. Accordingly, currently, the
thin film transistor liquid crystal display is applied to a notebook
computer, a wall-mounted television and the like, and the application
range thereof is expanded.

[0004] During the production of a typical color thin film
transistor-liquid crystal display, a thin film transistor driving device
and an ITO transparent electrode are layered on a glass substrate, and an
alignment film is then layered thereon to form a lower substrate of a
cell. Spacers are formed by using a silant in order to inject a liquid
crystal material between inner surfaces of a pair of upper and lower
substrates, polarized films are provided on outer surfaces of the glass
substrates, and the liquid crystal material is injected between a pair of
substrates and cured to produce a liquid crystal display cell.

[0005] In the TFT-LCD, in order to use the liquid crystal as an optical
switch, it is required that the liquid crystal is initially aligned on
the layer on which the thin film transistor is formed at the innermost
part of the display cell in a predetermined direction. In order to
achieve this, a liquid crystal alignment film is used.

[0006] As a method of preparing the alignment film, a rubbing treatment
method of unidirectionally rubbing a polymer resin film made of a
polyimide or the like formed on a substrate by using clothes or a method
of inclinedly depositing silicon dioxide (SiO2) is known. In the
case of the alignment film that is prepared by using the rubbing
treatment method, there are problems in that the contamination is caused
by the impurity that may be generated due to contact during the rubbing,
the yield of the products is reduced due to the occurrence of static
electricity, and contrast is reduced. In the case of the method of
inclinedly depositing silicon dioxide, there are problems in that the
preparing cost is increased and it is difficult to form the film having a
large area, thus, the film is not suitable to be applied to a large
liquid crystal display.

[0007] In order to solve this, an alignment method by a non-rubbing
process using a photopolymerizable alignment material is developed to
perform a photopolymerization by using the radiation of light so that the
alignment of polymer is induced to align liquid crystals. A
representative example of the non-rubbing process is an optical alignment
using photopolymerization that is announced by M. Schadt, et al. (Jpn. J.
Appl. Phys., Vol 31, 1992, 2155), Dae S. Kang, et al. (U.S. Pat. No.
5,464,669), and Yuriy Reznikov (Jpn. J. Appl. Phys. Vol. 34, 1995,
L1000). The optical alignment is a mechanism in which a photoreaction of
a photosensitive group that is connected to the polymer occurs due to
linearly polarized ultraviolet rays, and in this procedure, a main chain
of the polymer is unidirectionally aligned, thereby aligning the liquid
crystals.

[0008] The polycinnamate-based polymer such as PVCN (poly(vinyl
cinnamate)) and PVMC (poly(vinyl methoxycinnamate)) has been mainly used
as a representative material of the photopolymerizable alignment film.
However, the polycinnamate-based polymer has a problem in that the
optical alignment property of the polymer is excellent but the thermal
stability is poor. That is, the thermal stability of the alignment film
depends on the thermal stability of the polymer, and since the main chain
of the polymer of polyvinyl cinnamate has a glass transition temperature
of 100° C. or less, there is a problem in that the thermal
stability of the alignment film is reduced.

[0009] Meanwhile, Japanese Unexamined Patent Application Publication No.
11-181127 discloses a method of producing a polymer type of alignment
film that has a main chain such as acrylate and methacrylate and a side
chain having a photosensitive group such as a cinnamate group, and an
alignment film that is produced by using the method. However, the patent
is disadvantageous in that since the mobility of the polymer is poor,
even though the polymer is exposed to light for a long time, it is
difficult to obtain the desired alignment property. The reason for this
is that since the photosensitive group which is present in the polymer is
restricted by the main chain of the polymer, the group is difficult to
rapidly react with the radiated polarized light. Accordingly, since a
long time is required to obtain a network polymer, a process efficiency
is reduced, and if an alignment treatment process is finished after an
insufficient time, since the alignment of the liquid crystals is
insufficient in the prepared liquid crystal display, there are problems
in that a dichroic ratio is low and contrast is reduced.

[0010] Korean Unexamined Patent Application Publication Nos. 2006-0029068
and 2004-0102862 disclose that polarized UV is radiated on a coated
liquid crystal material without using a rubbing process to determine an
alignment direction of liquid crystal. However, as described in the above
patent, in the case of when the polarized UV is radiated on a curable
liquid crystal material to align the liquid crystal, since the curing of
the liquid crystal occurs in an alignment direction, the insufficient
curing occurs, thus reducing the surface strength and easily causing the
deformation due to external impact or heat.

[0011] Accordingly, a demand for a novel photoreactive polymer that has
the excellent thermal stability and the improved surface strength and
photoreaction rate is growing.

DISCLOSURE OF THE INVENTION

Technical Problem

[0012] The present invention has been made keeping in mind the above
problems occurring in the related art, and it is an object of the present
invention to provide a compound that has the excellent thermal stability
and the improved photoreaction rate and is capable of being used as a
monomer of the photoreactive polymer.

[0013] It is another object of the present invention to provide a
photoreactive polymer that includes the compound.

[0014] It is still another object of the present invention to provide a
method of preparing the photoreactive polymer.

Technical Solution

[0015] In order to accomplish the above objects, the present invention
provides a multi-cyclic compound that includes a photoactive functional
group in a main chain.

[0016] Additionally, the present invention provides a ring-opened
hydrogenated polymer that includes the multi-cyclic compound as a
monomer.

[0017] Additionally, the present invention provides a photoreactive
polymer that includes a cycloolefin-noncycloolefin in a main chain.

[0018] Additionally, the present invention provides a method of preparing
a ring-opened hydrogenated polymer that includes the multi-cyclic
compound as a monomer. The method includes polymerizing the multi-cyclic
compound in the presence of a catalyst mixture that includes a
procatalyst including Group 4, Group 6, and Group 8 transition metals, a
cocatalyst that provides a Lewis base capable of being weakly coordinate
bonded to the metal of the procatalyst, and activators including neutral
Group 15 and Group 16 elements that selectively improve the activity of
the procatalyst metal at a temperature in the range of 10 to 200°
C. while linear alkene, which is capable of controlling a size of a
molecular weight, is added, and adding a catalyst that includes Group 4
or Group 8 to Group 10 transition metals to add hydrogen to a double bond
remaining on a main chain.

[0019] Additionally, the present invention provides a method of preparing
a polymer that includes a cycloolefin-noncycloolefin in a main chain. The
method includes copolymerizing a cycloolefin monomer and a noncycloolefin
monomer in conjunction with the noncyclic monomer by using a metallocene
catalyst while a ring of the cyclic monomer is not opened. The
copolymerizing is performed in the presence of a catalyst mixture that
consists of a procatalyst including a metallocene catalyst and a
cocatalyst including aluminoxane at a temperature in the range of 10 to
200° C. under polymerization pressure in the range of 1 to 60 bar.

Advantageous Effects

[0020] Since a photoreactive polymer according to the present invention
includes a multi-cyclic compound having a high glass transition
temperature as a main chain, the thermal stability is excellent, and
since the mobility of the main chain is relatively high as compared to
that of an additional polymer, a photoreactive group can be freely moved
in the main chain of the polymer. Accordingly, it is possible to overcome
a slow photoreactive rate that is considered a disadvantage of a polymer
material used to prepare an alignment film for known liquid crystal
display devices. In addition, in the case of the photoreactive polymer
that includes the cycloolefin-noncycloolefin, the surface strength that
cannot be improved by using the multi-cyclic compound can be improved by
introducing the noncycloolefin compound into the main chain.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 is a graph that illustrates the measurement of light leakage
of a liquid crystal retardation film that is prepared in Preparation
Example 1 and Comparative Example 2; and

[0022] FIG. 2 is a graph that illustrates the measurement of light leakage
of a retardation film that is prepared in Preparation Example 4 and
Comparative Example 3.

BEST MODE FOR CARRYING OUT THE INVENTION

[0023] Hereinafter, a detailed description will be given of the present
invention.

[0024] A multi-cyclic compound having a photoactive functional group
according to the present invention is a compound that is represented by
the following Formula 1.

##STR00001##

[0025] In the above Formula 1, P is an integer in the range of 0 to 4, and

[0026] at least one of R1, R2, R3, and R4 is a radical
that is selected from the group consisting of the following Formulae 1a,
1b, and 1c and the remains are each independently selected from the group
consisting of hydrogen; halogen; substituted or unsubstituted C1-C20
alkyl; substituted or unsubstituted C2-C20 alkenyl; substituted or
unsubstituted C5-C12 cycloalkyl; substituted or unsubstituted C6-C40
aryl; substituted or unsubstituted C7-C15 aralkyl; substituted or
unsubstituted C2-C20 alkynyl; and a non-hydrocarbonaceous polar group
that includes one or more elements selected from the group consisting of
oxygen, nitrogen, phosphorus, sulfur, silicon, and boron, if R1,
R2, R3, and R4 are not hydrogen, halogen, or a polar
functional group, R1 and R2 or R3 and R4 may be
bonded to each other to form a C1-C10 alkylidene group, or R1 or
R2 may be bonded to any one of R3 and R4 to form a
saturated or unsaturated C4-C12 ring or an aromatic ring having 6 to 24
carbon atoms, specific examples of the non-hydrocarbonaceous polar group
include, but are not limited to --OR6, --R5OR6,
--OC(O)OR6, --R5OC(O)OR6, --C(O)OR6,
--R5C(O)OR6, --C(O)R6, --R5C(O)R6,
--OC(O)R6, --R5OC(O)R6, --(R5O)p--OR6 (p is
an integer in the range of 1 to 10), --(OR5)p--OR6 (p is
an integer in the range of 1 to 10), --C(O)--O--C(O)R6,
--R5C(O)--O--C(O)R6, --SR6, --R5SR6,
--SSR6, --R5SSR6, --S(═O)R6,
--R5S(═O)R6, --R5C(═S)R6,
--R5C(═S)SR6, --R5SO3R6, --SO3R6,
--R5N═C═S, --N═C═S, --NCO, --R5--NCO, --CN,
--RCN, --NNC(═S)R6, --R5NNC(═S)R6, --NO2,
--R5NO2,

##STR00002## ##STR00003## ##STR00004##

[0027] R5 of each of the functional groups is substituted or
unsubstituted C1-C20 alkylene; substituted or unsubstituted C2-C20
alkenylene; substituted or unsubstituted C5-C12 cycloalkylene;
substituted or unsubstituted C6-C40 arylene; substituted or unsubstituted
C7-C15 aralkylene; or substituted or unsubstituted C2-C20 alkynylene, and

[0034] R10, R11, R12, and R13 are each independently
selected from the group consisting of substituted or unsubstituted C1-C20
alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or
unsubstituted C6-C30 aryloxy, and substituted or unsubstituted C6-C40
aryl; and

[0035] C is C6-C40 aryl; or C6-C40 hetero aryl that includes Group 14, 15
or 16 hetero elements (S, O, N or the like), and the aryl or hetero aryl
is substituted with substituted or unsubstituted C1-C20 alkoxy or
substituted or unsubstituted C6-C30 aryloxy. Representative examples of C
include, but are not limited to, compounds that are represented by the
following Formula 2.

##STR00006##

[0036] In Formulae 1c and 2, at least one of R'10, R'11,
R'12, R'13, R'14, R'15, R'16, R'17, and
R'18 is necessarily substituted or unsubstituted C1-C20 alkoxy or
substituted or unsubstituted C6-C30 aryloxy, and the remains are each
independently hydrogen, substituted or unsubstituted C1-C20 alkyl,
substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted
C6-C30 aryloxy, or substituted or unsubstituted C6-C40 aryl.

[0037] In the present invention, an experiment in which a polarizer is
disposed in front of a UV lamp to directly radiate the polarized UV to
the alignment film is performed. In respects to the spectrum of the
polarized UV, the intensity of light is significantly reduced at 300 nm
or less, and the peak at around 365 nm is highest among the peaks that
are most close to ultraviolet rays. Meanwhile, the UV absorption of the
polymers that are aryl or heteroaryl in which C is substituted with the
alkoxy group or the aryloxy group is red-shifted as compared to the
polymers that are aryl in which C is substituted with hydrogen or the
alkyl group. Accordingly, it is expected that the photoreaction rapidly
occurs in the case of the polymers having the absorption spectrum that is
close to the highest peak of UV in comparison with the cases of the other
polymers.

[0038] In addition, the polymers that are aryl or heteroaryl in which C is
substituted with the alkoxy group or the aryloxy group have increased
compatibility in respects to the liquid crystals, thus directly affecting
the alignment of the liquid crystals and significantly affecting the
quality of the liquid crystal retardation film finally obtained.

[0039] The photoreactive ring-opened hydrogenated polymer that includes
the multi-cyclic compound according to the present invention as the
monomer in the main chain may include a repeating unit that is
represented by the following Formula 3.

##STR00007##

[0040] In Formula 3,

[0041] n is in the range of 50 to 5,000, and

[0042] P, R1, R2, R3, and R4 are the same as those
defined in the above.

[0043] In addition, the ring-opened hydrogenated polymer that includes the
multi-cyclic compound according to the present invention as a monomer may
further include one or more of the multi-cyclic compounds that are
represented by the following Formula 4 as the monomer:

##STR00008##

[0044] In Formula 4,

[0045] P' is an integer in the range of 0 to 4,

[0046] R'1, R'2, R'3, and R'4 are each independently
selected from the group consisting of hydrogen; halogen; substituted or
unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl;
substituted or unsubstituted C5-C12 cycloalkyl; substituted or
unsubstituted C6-C40 aryl; substituted or unsubstituted C7-C15 aralkyl;
substituted or unsubstituted C2-C20 alkynyl; and a non-hydrocarbonaceous
polar group that includes one or more elements selected from the group
consisting of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron,

[0047] if R'1, R'2, R'3, and R'4 are not hydrogen,
halogen, or a polar functional group, R'1, and R'2, or R'3
and R'4 may be bonded to each other to form a C1-C10 alkylidene
group, or R'1 or R'2 may be bonded to any one of R'3 and
R'4 to form a saturated or unsaturated C4-C12 ring or an aromatic
ring having 6 to 24 carbon atoms, specific examples of the
non-hydrocarbonaceous polar group include, but are not limited to
-OR6, --R5OR6, --OC(O)OR6, --R5OC(O)OR6,
--C(O)OR6, --R5C(O)OR6, --C(O)R6,
--R5C(O)R6, --OC(O)R6, --R5OC(O)R6,
--(R5O)p--OR6 (p is an integer in the range of 1 to 10),
--(OR5)p--OR6 (p is an integer in the range of 1 to 10),
--C(O)--O--C(O)R6, --R5C(O)--O--C(O)R6, --SR6,
--R5SR6, --SSR6, --R5SSR6, --S(═O)R6,
--R5S(═O)R6, --R5C(═S)R6,
--R5C(═S)SR6, --R5SO3R6, --SO3R6,
--R5N═C═S, --N═C═S, --NCO, --R5--NCO, --CN,
--R5CN, --NNC(═S)R6, --R5NNC(═S)R6,
--NO2, --R5NO2,

##STR00009## ##STR00010## ##STR00011##

[0048] R5 of each of the functional groups is substituted or
unsubstituted C1-C20 alkylene; substituted or unsubstituted C2-C20
alkenylene; substituted or unsubstituted C5-C12 cycloalkylene;
substituted or unsubstituted C6-C40 arylene; substituted or unsubstituted
C7-C15 aralkylene; or substituted or unsubstituted C2-C20 alkynylene, and

[0050] The definition of the above-mentioned substituent groups will be
described in detail.

[0051] The term "alkyl" means a straight- or branched-chained saturated
monovalent hydrocarbon portion having 1 to 20 carbon atoms, preferably 1
to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. The alkyl
group may be arbitrarily substituted with one or more halogen
substituents. Examples of the alkyl group include methyl, ethyl, propyl,
2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl,
fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,
dichloromethyl, trichloromethyl, iodomethyl, bromomethyl and the like.

[0052] The term "alkenyl" means a straight- or branched-chained monovalent
hydrocarbon portion having 2 to 20 carbon atoms, preferably 2 to 10
carbon atoms, and more preferably 2 to 6 carbon atoms having one or more
carbon-carbon double bonds. The alkenyl group may be bonded through the
carbon atoms having the carbon-carbon double bonds or the saturated
carbon atoms. The alkenyl group may be arbitrarily substituted with one
or more halogen substituents. Examples of the alkenyl group may include
ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl,
5-hexenyl, dodecenyl and the like.

[0053] The term "cycloalkyl" means a saturated or unsaturated nonaromatic
monovalent monocyclic, bicyclic or tricyclic hydrocarbon portion having 5
to 12 cyclic carbons, and may be arbitrarily substituted with one or more
halogen substituents. Examples of the cycloalkyl may include cyclopropyl,
cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,
cycloheptyl, cyclooctyl, decahydronaphthalenyl, adamantyl, norbornyl
(that is, bicyclo[2.2.1]hept-5-enyl) or the like.

[0054] The term "aryl" means a monovalent monocyclic, bicyclic or
tricyclic aromatic hydrocarbon portion having 6 to 20 ring atoms, and
preferably 6 to 12 ring atoms, and may be arbitrarily substituted with
one or more halogen substituents and the like. The aromatic portion of
the aryl group includes only a carbon atom. Examples of the aryl group
may include phenyl, naphthalenyl, fluorenyl and the like.

[0055] The term "alkoxyaryl" means one or more hydrogen atoms of the aryl
group defined as described above, which are substituted with the alkoxy
group. Examples of the alkoxyaryl group may include methoxyphenyl,
ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hetoxy phenyl,
heptoxy phenyl, octoxyphenyl, nanoxyphenyl, methoxybiphenyl,
ethoxybiphenyl, propoxybiphenyl, methoxynaphthalenyl, ethoxynaphthalenyl,
propoxynaphthalenyl, methoxyanthracenyl, ethoxyanthracenyl,
propoxyanthracenyl, methoxyfluorenyl and the like.

[0056] The term "araryl" means one or more hydrogen atoms of the alkyl
group defined as described above, which are substituted with the aryl
group. The aralkyl may be arbitrarily substituted with one or more
halogen substituents. Examples of the aralkyl may include benzyl,
benzhydril, tritile and the like.

[0057] The term "alkynyl" means a straight- or branched-chained monovalent
hydrocarbon portion having 2 to 20 carbon atoms, preferably 2 to 10
carbon atoms, more preferably 2 to 6 carbon atoms having one or more
carbon-carbon triple bonds. The alkynyl group may be bonded through the
carbon atoms having the carbon-carbon triple bonds or the saturated
carbon atoms. The alkynyl group may be arbitrarily substituted with one
or more halogen substituents. Examples of the alkynyl group may include
ethynyl, propynyl and the like.

[0058] The term "alkylene" means a straight- or branched-chained divalent
saturated hydrocarbon portion having 1 to 20 carbon atoms, preferably 1
to 10 carbon atoms, more preferably 1 to 6 carbon atoms. The alkylene
group may be arbitrarily substituted with one or more halogen
substituents. Examples of the alkyl group may include methylene,
ethylene, propylene, butylene, hexylene and the like.

[0059] The term "alkenylene" means a straight- or branched-chained
divalent hydrocarbon portion having 2 to 20 carbon atoms, preferably 2 to
10 carbon atoms, more preferably 2 to 6 carbon atoms having one or more
carbon-carbon double bonds. The alkenylene group may be bonded through
the carbon atoms having the carbon-carbon double bonds and/or the
saturated carbon atoms. The alkenylene group may be arbitrarily
substituted with one or more halogen substituents.

[0060] The term "cycloalkylene" means a saturated or unsaturated
nonaromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon
portion having 5 to 12 cyclic carbons, and may be arbitrarily substituted
with one or more halogen substituents. Examples of the cycloalkylene may
include cyclopropylene, cyclobutylene and the like.

[0061] The term "arylene" means a divalent monocyclic, bicyclic or
tricyclic aromatic hydrocarbon portion having 6 to 20 cyclic atoms and
preferably 6 to 12 cyclic atoms, and may be arbitrarily substituted with
one or more halogen substituents. The aromatic portion of the aryl group
includes only the carbon atoms. Examples of the arylene group may include
phenylene and the like.

[0062] The term "aralkylene" means a divalent portion in which one or more
hydrogen atoms of the alkyl group defined as described above are
substituted with the aryl group, and may be arbitrarily substituted with
one or more halogen substituents. Examples of the aralkylene may include
benzylene and the like.

[0063] The term "alkynylene" means a straight- or branched-chained
divalent hydrocarbon portion having 2 to 20 carbon atoms, preferably 2 to
10 carbon atoms, more preferably 2 to 6 carbon atoms having one or more
carbon-carbon triple bonds. The alkynylene group may be bonded through
the carbon atoms having the carbon-carbon triple bonds or the saturated
carbon atoms. The alkynylene group may be arbitrarily substituted with
one or more halogen substituents. Examples of the alkynylene group may
include ethynylene, propynylene and the like.

[0064] The term "bond" means a bonding portion while no substituent group
is inserted.

[0065] In respects to the multi-cyclic compound ring-opened hydrogenated
polymer that includes the photoactive functional group, linear alkene
such as 1-alkene, 2-alkene and the like, which is capable of controlling
a size of a molecular weight, is added in an amount of 1 to 100 mol %
based on the monomer in the presence of a catalyst mixture that consists
of a procatalyst including Group 4 (for example, Ti, Zr, Hf), Group 6
(for example, Mo, W), and Group 8 (for example, Ru, Os) transition metal,
a cocatalyst that provides a Lewis base capable of being weakly
coordinate bonded to the metal of the procatalyst, and neutral Group 15
and Group 16 activators that selectively improve the activity of the
procatalyst metal, the polymerization is performed at a temperature in
the range of 10 to 200° C. After that, a catalyst that includes
Group 4 (for example, Ti, Zr) or Group 8 to Group 10 (for example, Ru,
Ni, Pd) transition metals is added in an amount of 1 to 30% by weight
based on the monomer to add hydrogen to the double bond remaining on the
main chain at the temperature in the range of 10 to 250° C.

[0066] In the case of when the reaction temperature is lower than
10° C., there is a problem in that the polymerization activity is
very low. In the case of when the reaction temperature is higher than
200° C., the catalyst may be decomposed, which is undesirable. In
the case of when the hydrogenation reaction temperature is lower than
10° C., there is a problem in that the activity of the
hydrogenation reaction is very low. In the case of when the hydrogenation
reaction temperature is higher than 250° C., the catalyst may be
decomposed, which is undesirable.

[0067] The catalyst mixture includes 1 to 100,000 mole of the cocatalyst
that provides a Lewis base capable of being weakly coordinate bonded to
the metal of the procatalyst based on 1 mole of the procatalyst that
includes Group 4 (for example, Ti, Zr, Hf), Group 6 (for example, Mo, W),
and Group 8 (for example, Ru, Os) transition metals, and selectively 1 to
100 mole of the activator that includes neutral Group 15 and Group 16
elements improving the activity of the procatalyst metal based on 1 mole
of the procatalyst.

[0068] In the case of when the content of the cocatalyst is less than 1
mole, there is a problem in that the activation of the catalyst is not
ensured. In the case of when the content of the cocatalyst is more than
100,000 mole, the activity of the catalyst is reduced, which is
undesirable. The activator may not be used according to the type of the
procatalyst. In the case of when the content of activator is less than 1
mole, there is a problem in that the activation of the catalyst is not
ensured. In the case of when the content of the activator is more than
100 mole, the molecular weight is reduced, which is undesirable.

[0069] In the case of when the content of the catalyst that includes the
Group 4 (for example, Ti, Zr) or Groups 8 to 10 (for example, Ru, Ni, Pd)
transition metals which are used during the hydrogenation reaction is
less than 1% by weight based on the monomer, there is a problem in that
the hydrogenation is not desirably performed. In the case of when the
content of the catalyst is more than 30% by weight, the polymer may be
discolored, which is undesirable.

[0070] The procatalyst that includes the Group 4 (for example, Ti, Zr,
Hf), Group 6 (for example, Mo, W), and Group 8 (for example, Ru, Os)
transition metals means a transition metal such as TiCl4, WCl6,
MoCl5, or RuCl3 having the functional group that easily
participates in the Lewis acid-base reaction to be separated from the
central metal while the metal is easily separated by the cocatalyst
providing the Lewis acid so that the central transition metal is
converted into the catalyst active species.

[0071] In addition, the cocatalyst providing the Lewis base that is
capable of being weakly coordination bonded to the metal of the
procatalyst may use borane or borate such as B(C6F5)3,
methyl aluminoxane (MAO), or alkylaluminum, alkylaluminum halide, or
aluminum halide such as Al(C2H5)3 and
Al(CH3)Cl2. Instead of aluminum, a substituent such as lithium,
magnesium, germanium, lead, zinc, tin, silicon and the like may be used.
The cocatalyst easily reacts with the Lewis base to form a vacancy of the
transition metal, and provides a compound that is weakly coordination
bonded to the transition metal compound or a compound providing the same
in order to stabilize the generated transition metal.

[0072] The activator for polymerization may be added, but may not be used
according to the type of the procatalyst. Examples of the activator that
includes the neutral Group 15 and Group 16 elements capable of improving
the activity of the procatalyst metal include water, methanol, ethanol,
isopropyl alcohol, benzyl alcohol, phemol, ethyl mercaptan,
2-chloroethanol, trimethylamine, triethylamine, pyridine, ethylene oxide,
benzoyl peroxide, t-butyl peroxide and the like.

[0073] The catalyst that includes the Group 4 (for example, Ti,Zr) or
Groups 8 to 10 (for example, Ru, Ni, Pd) transition metals used during
the hydrogenation reaction may be present in a homogeneous form that can
be immediately mixed with a solvent or a substance in which the metal
catalyst complex compound is carried in a fine supporting material.
Preferable examples of the fine supporting material include silica,
titania, silica/chromia, silica/chromia/titania, the silica/alumina, an
aluminum phosphate gel, silanized silica, silica hydrogel, montmorilonite
clay, and zeolite.

[0074] According to an embodiment of the present invention, the catalyst
mixture that consists of a procatalyst including Group 4, Group 6, and
Group 8 transition metals, a cocatalyst that provides a Lewis base
capable of being weakly coordinate bonded to the metal of the
procatalyst, and neutral Group 15 and Group 16 activators that
selectively improve the activity of the procatalyst metal is prepared.
Additionally, linear alkene may be further added to control the size of
the molecular weight. Next, the monomer solution that includes the
multi-cyclic compound having the photoactive functional group is
subjected to the ring-opened polymerization in the presence of the
organic solvent and the catalyst mixture and then subjected to the
hydrogenation reaction. However, the order of the addition of the
catalyst, the monomer, and the solvent is not limited.

[0075] A photoreactive polymer according to another embodiment of the
present invention is a cycloolefin-noncycloolefin polymer that includes a
repeating unit represented by the following Formula 5.

##STR00012##

[0076] In Formula 5,

[0077] n is the degree of polymerization in the range of 50 to 5000,

[0078] the content of the repeating unit of cycloolefin that is
represented by x is in the range of 0.1 to 99.9 mol %,

[0079] the content of the repeating unit of linear olefin that is
represented by y is in the range of 0.1 to 99.9 mol %,

[0080] the content of the repeating unit of cycloolefin that is
represented by z is in the range of 0.1 to 99.9 mol %,

[0081] the order of the repeatition of noncycloolefin and cycloolefin is
random,

[0082] P, R1, R2, R3, and R4 are the same as those
defined in Formula 1,

[0083] Ra is a hydrogen atom or a C1-C20 hydrocarbon group, and

[0084] P', R1', R2', R3', and R4' are the same as
those defined in Formula 4.

[0085] The "hydrocarbon group in Ra" includes alkyl, cycloalkyl, alkylene,
and cycloalkylene as defined above, for example, α-olefin,
butadiene, and pentadiene, and definitions of the other substituent
groups are the same as those of the case of the photoreactive ring-opened
hydrogenated polymer.

[0086] Hereinafter, a method of preparing the polymer that is used to form
the alignment film will be described.

[0087] The cycloolefin-noncycloolefin polymer that includes the
photoactive functional group is prepared by performing the polymerization
in the presence of a catalyst mixture that consists of a procatalyst
including the metallocene catalyst and a cocatalyst including aluminoxane
at a temperature in the range of 10 to 200° C. under
polymerization pressure in the range of 1 to 60 bar.

[0088] In the case of when the reaction temperature is less than
10° C., there is a problem in that the polymerization activity is
very low. In the case of when the reaction temperature is higher than
200° C., the catalyst may be decomposed, which is undesirable.

[0089] Preferable examples of the procatalyst include the metallocene
catalyst. Examples of the metallocene catalyst include a metallocene
catalyst such as rac-ethylene-bis-(1-indenyl)-zirconiumdichloride,
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconiumdichloride,
rac-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride,
phenylmethyl-(9-fluorenyl)-cyclopentadienyl zirconium dichloride,
rac-dimethylgermyl-bis-(1-indenyl)-zirconium dichloride,
rac-phenylmethylsilyl-bis-(1-indenyl)-zirconium dichloride, and
rac-phenylvinylsilyl-bis-(1-indenyl)-zirconium dichloride.

[0090] In addition, preferable examples of the cocatalyst include
aluminoxane, and examples of aluminoxane include methyl aluminoxane,
ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like.

[0091] In general, the transition metal compound (catalyst and cocatalyst)
is previously activated in a solution. The concentration of aluminoxane
that is present in a solution state is generally in the range of 1 wt %
to the saturation concentration. Metallocene may be used at the same
concentration, but it is preferable to use 10-4 to 10-2 mol of
metallocene based on 1 mole of aluminoxane. The previous activation time
is preferably in the range of 15 to 60 min, and at this time, the
temperature is in the range of 15 to 70° C. In addition, it is
preferable that the metallocene compound be generally used in an amount
of 10-4 to 10-6 mole per 1 L of the volume of the reactor based
on the transition metal. It is preferable that aluminoxane be used in an
amount of 104 mole per 1 L of the volume of the reactor based on the
aluminum (Al). The incorporation ratio of the monomers depends on the
polymerization conditions such as the reaction temperature, the reaction
pressure, the concentration of the catalyst, the concentration of the
cocatalyst and the like. It is preferable that the incorporation ratio of
the cyclic monomer be in the range of 10 to 80 mol %.

[0092] The photoreactive polymer according to the present invention may be
used to prepare an alignment film for liquid crystal display devices by
applying the solution of the monomer on a substrate having a transparent
electrode, removing a solvent to form a film, and radiating ultraviolet
rays polarized in a predetermined direction thereon to provide an
anisotropic property on the surface of the film.

MODE FOR THE INVENTION

[0093] A better understanding of the present invention may be obtained in
light of the following Examples which are set forth to illustrate, but
are not to be construed to limit the present invention.

[0094] In addition, in the following Examples, all the operations in which
the compounds that were sensitive to air or water were treated were
performed by using the standard Schlenk technique or the dry box
technique. The nuclear magnetic resonance (NMR) spectrum was obtained by
using the Bruker 300 spectrometer. In connection with this, the 1H
NMR was measured at 300 MHz and the 13C NMR was measured at 75 MHz.
The molecular weight and the molecular weight distribution of the
ring-opened hydrogenated polymer were measured by using the GPC (gel
permeation chromatography). In connection with this, the polystyrene
sample was used as the standard sample.

[0095] Toluene was subjected to the distillation in potassium/benzophenone
to be purified, and dichloromethane was subjected to the purification in
CaH2 by the distillation.

Preparing of the Photoreactive Ring-Opened Hydrogenated Polymer Including
the Multi-Cyclic Compound

[0096] DCPD (dicyclopentadiene, Aldrich, 397 g, 3 mol), and aryl alcohol
(Aldrich, 331 g, 5.7 mol) were put into the high pressure reactor having
the volume of 2 L and then heated to 210° C. The agitation was
performed at 300 rpm to conduct the reaction for 1 hour. When the
reaction was finished, the reactant was cooled and then moved to the
distillation device. The distillation was performed twice under reduced
pressure of 1 torr by using the vacuum pump to obtain the product at 56 t
(yield: 52%).

(2) The Ring Opening Metathesis Polymerization and the Hydrogenation
Reaction of 5-norbornene-2-methanol

[0098] 6.20 g (50 mmol) of 5-norbornene-2-methanol that was synthesized in
(1) was punt into the Schlenk flask having the volume of 250 ml under an
Ar atmosphere, and 34 g of toluene that was purified by using the solvent
was added thereto. 11.4 mg (1.0 mmol) of triethyl aluminum (TEA) that was
the cocatalyst was first added thereto while the flask was maintained at
the polymerization temperature of 80° C. Subsequently, 1 ml of the
0.01 M (mol/L) toluene solution (WCl6 0.01 mmol, ethanol 0.03 mmol)
in which tungsten hexachloride (WCl6) and ethanol were mixed with
each other at a ratio in the range of 1:3 was added to the flask.
Finally, 0.84 g of 1-octene (7.5 mmol) that was the molecular weight
controlling agent was added to the flask and then reacted at 80°
C. for 18 hours while the agitation was performed. After the reaction was
finished, ethyl vinyl ether that was the polymerization terminator was
dropped on the polymerization solution in a small amount and the
agitation was then performed for 5 minutes.

[0099] The polymerization solution was transported to the high pressure
reactor having the volume of 300 mL, and 0.06 ml of triethyl aluminum
(TEA) was added thereto. Subsequently, 0.50 g of grace raney Nickel
(slurry phase in water) was added thereto, and the reaction was performed
while the pressure of hydrogen was maintained at 80 atm and the agitation
was performed at 150° C. for 2 hours. After the reaction was
finished, the polymerization solution was dropped on acetone to perform
the precipitation, and the precipitate was filtered and then dried in a
vacuum oven at 70° C. for 15 hours to obtain 5.62 g of ring-opened
hydrogenated polymer of 5-norbornene-2-methanol (yield=90.6%, Mw=69,900,
Mw/Mn=4.92).

(3) Synthesis of 4-methoxy cinnamoyl chloride

[0100] 25 g of the 4-methoxy benzoic acid) (166.5 mmol) and 69.35 g of
SOCl2 (582.8 mmol) were put into the round-bottomed flask having the
volume of 250 ml, and then agitated at normal temperature for 18 hours.
After the reaction was finished, the reduced pressure was applied to
remove an excessive amount of SOCl2, and the reactant was diluted
with 150 ml of toluene and neutralized by using the NaHCO3 solution
(100 ml×3). Water was removed from the neutralized toluene solution
by using MgSO4 and the solvent was removed under reduced pressure to
obtain 31.1 g of 4-methoxy cinnamoyl chloride that was the white solid
(yield=95%).

[0101] The ring-opened hydrogen additional polymer (15 g, 0.121 mol) of
5-norbornene-2-methanol that was synthesized in (2), triethylamine
(Aldrich, 61.2 g, 0.605 mol), 50 ml of THF were put into the 2-neck flask
having the volume of 250 ml, and then agitated in the 0° C.
ice-water bath. 4-methoxy cinnamoyl chloride (22.1 g, 0.133 mol) that was
synthesized in (3) was dissolved in 60 ml of THF, and slowly added by
using the additional flask. After 10 minutes, the temperature of the
reactant was increased to normal temperature and the additional agitation
was performed for 18 hours. The solution was diluted with ethyl acetate,
transported to the separatory funnel, and washed several times by using
water and NaHCO3. The reaction solution was dropped in acetone to
perform the precipitation, and the precipitate was filtered and then
dried in a vacuum oven at 70° C. for 15 hours (yield: 94%).

(1) Synthesis of the Ring-Opened Hydrogenated Polymer of the
5-norbornene-2-carboxylic acid

[0102] 11.0 g (79.64 mmol) of the 5-norbornene-2-carboxylic acid was put
into the Schlenk flask having the volume of 250 ml under an Ar
atmosphere, and 55 g of toluene that was purified by using the solvent
was added thereto. 18.2 mg (1.6 mmol) of triethyl aluminum (TEA) that was
the cocatalyst was first added thereto while the flask was maintained at
the polymerization temperature of 80° C. Subsequently, 1.6 ml of
the 0.01 M (mol/L) toluene solution (WCl6 0.016 mmol, ethanol 0.048
mmol) in which tungsten hexachloride (WCl6) and ethanol were mixed
with each other at a ratio in the range of 1:3 was added to the flask.
Finally, 1.34 g of 1-octene (11.95 mmol) that was the molecular weight
controlling agent was added to the flask and then reacted at 80°
C. for 18 hours while the agitation was performed. After the reaction was
finished, ethyl vinyl ether that was the polymerization terminator was
dropped on the polymerization solution in a small amount and the
agitation was then performed for 5 minutes.

[0103] The polymerization solution was transported to the high pressure
reactor having the volume of 300 mL, and 0.38 ml of triethyl aluminum
(TEA) was added thereto. Subsequently, 3.20 g of grace raney Nickel
(slurry phase in water) was added thereto, and the reaction was performed
while the pressure of hydrogen was maintained at 80 atm and the agitation
was performed at 150° C. for 2 hours. After the reaction was
finished, the polymerization solution was dropped on acetone to perform
the precipitation, and the precipitate was filtered and then dried in a
vacuum oven at 70° C. for 15 hours to obtain 10.1 g of ring-opened
hydrogenated polymer of 5-norbornene-2-carboxylic acid (yield=92%,
Mw=71,500, Mw/Mn=4.51).

[0104] 10.1 g of the ring-opened hydrogenated polymer of the
5-norbornene-2-carboxylic acid that was synthesized in (1) (71.55 mmol),
16.52 g of 4'-hydroxy-4-methoxychalcone) (65.0 mmol), 19.9 g of
EDC(N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride)
(Aldrich, 104.2 mmol), and 13.2 g of HOBT (1-Hydroxybenzotriazole
hydrate) (Aldrich, 97.52 mmol) were sequentially put into the two-neck
flask having the volume of 250 ml, and then dissolved in 100 ml of DMF.
After the temperature was reduced to 0° C., triethylamine
(Aldrich, 45 ml, 325 mmol) was slowly dropped. After the temperature was
increased to normal temperature and maintained overnight. When the
reaction was finished, the extraction was performed by using a great
amount of ethyl acetate. The resulting substance was washed by using
NaHCO3 and H2O, the reaction solution was dropped on acetone to
perform the precipitation, and the precipitate was filtered and then
dried in a vacuum oven at 70° C. for 15 hours to obtain 9.4 g of
ring-opened hydrogenated polymer of
5-norbornene-2-(4'-hydroxy-4-methoxychalcone) ester (yield=93%).

[0105] 10.1 g of the ring-opened hydrogenated polymer of the
5-norbornene-2-carboxylic acid that was synthesized in (1) of Example 2
(71.55 mmol), 12.49 g of 7-hydroxy-6-methoxycoumarin (Aldrich, 65.0
mmol), 19.9 g of EDC(N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide
hydrochloride) (Aldrich, 104.2 mmol), and 13.2 g of HOBT
(1-Hydroxybenzotriazole hydrate) (Aldrich, 97.52 mmol) were sequentially
put into the two-neck flask having the volume of 250 ml, and then
dissolved in 100 ml of DMF. After the temperature was reduced to
0° C., triethylamine (Aldrich, 45 ml, 325 mmol) was slowly
dropped. After the temperature was increased to normal temperature and
maintained overnight. When the reaction was finished, the extraction was
performed by using a great amount of ethyl acetate. The resulting
substance was washed by using NaHCO3 and H2O, the reaction
solution was dropped on acetone to perform the precipitation, and the
precipitate was filtered and then dried in a vacuum oven at 70° C.
for 15 hours to obtain 9.4 g of ring-opened hydrogenated polymer of
5-norbornene-2-(7-hydroxy-6-methoxy coumarine)ester (yield=93%).

Example 4

Synthesis of the Ring-Opened Hydrogenated Polymer to which the 4-propoxy
cinnamoyl Group was Introduced

(1) The Ring-Opened Hydrogenated Polymerization and the Hydrogenation
Reaction of METCD

[0106] 13.2 g of 8-methoxy-carbonyl tetracyclo[4, 4, 0, 12, 5, 17,
10]dode-3-cene (METCD) (0.1 mol) as the monomer, 1.1 g of 1-octene (10
mmol), and 60 ml of toluene that was purified by using the solvent were
put into the schlenk flask having the volume of 250 ml. 0.02 mmol of
WCl6 that was dissolved in 1 ml of toluene and 0.14 mmol of
triethylaluminum were put into the flask as the catalyst, and the
reaction was performed while the agitation was performed at 80° C.
for 18 hours. After the reaction was performed for 18 hours, the reactant
was added to an excessive amount of acetone to obtain a ring-opened
polymer precipitate. The ring-opened polymer that was obtained by
filtering the precipitate using the glass funnel was dried in a vacuum
oven at 70° C. for 24 hours to obtain 11.8 g of the METCD
ring-opened polymer (yield: 90%).

[0107] 15 g of the synthesized METCD ring-opened polymer, and 150 ml of
toluene as the solvent were added to the high pressure reactor having the
volume of 300 ml. 70 ppm of [RuHCl(CO)(PCy3)3] was added as the
catalyst to the reactor, the hydrogen pressure of 10 Mpa was applied, and
the agitation was performed at 165° C. for 4 hours to perform the
hydrogenation reaction. After the reaction was finished, the hydrogen
pressure was removed, and the reactant was added to an excessive amount
of ethanol to obtain a ring-opened hydrogenated polymer precipitate. The
polymer that was obtained by filtering the precipitate using the glass
funnel was dried in a vacuum oven at 70° C. for 24 hours to obtain
the ring-opened hydrogenated polymer (hydrogenation ratio: 99.7%,
Mw=76,800, Mw/Mn=4.38).

(2) The Reduction Reaction of the METCD Ring-Opened Hydrogenated Polymer

[0108] The METCD ring-opened hydrogenated polymer (22 g, 0.1 mol) that was
synthesized in (1), and 100 ml of THF were put into the 2-neck flask
having the volume of 250 ml, and then agitated in the 0° C.
ice-water bath. Lithiumaluminum hydride (LiAlH4) (Aldrich, 4.2 g, 0.11
mol) was dissolved in 10 ml of THF, and slowly added to the reactant by
using the additional flask. After 2 hours, the temperature of the
reactant was increased to normal temperature and the additional agitation
was performed for 3 hours. The reaction solution was precipitated in a
large amount of ethanol to obtain 15.4 g of the ring-opened hydrogenated
polymer (ring-opened hydrogenated polymer of TCD-CH2OH) in which the
ester functional group of METCD was reduced to alcohol (yield: 70%).

(3) Synthesis of the Ring-Opened Hydrogenated Polymer to which the
4-propoxy cinnamoyl group was Introduced (esterification of the
Ring-Opened Hydrogenated Polymer of TCD-CH2OH)

[0109] The TCD-CH2OH ring-opened hydrogenated polymer (2.3 g, 12.1
mmol) that was synthesized in (2), 4-propoxy cinnamic acid (2.49 g, 12.1
mmol), EDC [1-(3-dimethylaminopropyl)-3-ethylcarboimide hydrochloride]
(Aldrich, 3.7 g, 19.4 mmol), and HOBT (1-hydroxybenzotriazole hydrate)
(Aldrich, 2.45 g, 18.2 mmol) were put into the 2-neck flask having the
volume of 250 ml, and then dissolved in 100 ml of DMF. Triethylamine
(Aldrich, 75 ml, 0.605 mol) was slowly dropped on the reaction solution.
After the agitation for 3 hours, when the reaction was finished, the
reaction solution was precipitated in a large amount of acetone to obtain
the ring-opened hydrogenated polymer to which the 4-propoxy cinnamoyl
group was introduced (yield: 97%).

Preparation Example 1

Preparation of the Alignment Film by using the
5-norbornene-2-methyl-4'-methoxy cinnamate Ring-Opened Hydrogenated
Polymer

[0110] The 5-norbornene-2-methyl-4'-methoxy cinnamate ring-opened
hydrogenated polymer that was synthesized in Example 1 was dissolved in
the c-pentanone solvent in a concentration of 2% by weight, and applied
on the polyethylene terephthalate substrate (commercial name: SH71,
prepared by SKC Co., Ltd. in Korea) having the thickness of 80 micron by
using the roll coating process so that the thickness of the polyethylene
terephthalate substrate was 1000 Å after the drying. Next, the
substrate was heated in an oven at 80° C. for 3 minutes to remove
the solvent in the inside of the coating film and to form the coating
film.

[0111] The exposing was performed by using a high pressure mercury lamp
having the intensity of 200 mW/cm2 as a light source while polarized
UV that was perpendicular to the proceeding direction of the film was
radiated on the coating film by using a Wire-grid polarizer prepared by
Moxtek, Co., Ltd. for 5 sec, so that the alignment was provided to form
the alignment film.

[0112] Next, the solid in which 95.0% by weight of cyanobiphenyl acrylate
that was polymerizable by UV and 5.0% by weight of Irgacure 907 (prepared
by Ciba-Geigy, Co., Ltd. in Switzerland) as the photoinitiator were mixed
with each other was dissolved in toluene so that the content of the
liquid crystal was 25 parts by weight based on 100 parts by weight of the
liquid crystal solution to prepare the polymerizable reactive liquid
crystal solution.

[0113] The prepared liquid crystal solution was applied on the
photo-alignment film that was formed by using a roll coating process so
that the thickness of the film after the drying was 1 μm, and the
drying was performed at 80° C. for 2 minutes to align the
molecules of the liquid crystal. The nonpolarized UV was radiated on the
aligned liquid crystal film by using a high-pressure mercury lamp having
the intensity of 200 mW/cm2 as a light source to fix the alignment
state of the liquid crystal, thereby preparing the retardation film.

[0114] The alignment properties in respects to the prepared retardation
film were compared to each other by measuring the light leakage between
the polarizing plates by the transmittance, and the quantitative
retardation value was measured by using Axoscan (prepared by Axomatrix,
Co., Ltd.).

Preparation Example 2

Preparation of the Alignment Film by using the
5-norbornene-2-(7-hydroxy-6-methoxy coumarine)ester Ring-Opened
Hydrogenated Polymer

[0115] The retardation film was prepared by using the same method as
Preparation Example 1, except that the
5-norbornene-2-(7-hydroxy-6-methoxy coumarine)ester ring-opened
hydrogenated polymer prepared in Example 3 was used instead of the
polymer prepared in Example 1.

Preparation Example 3

Preparation of the Alignment Film by using the Ring-Opened Hydrogenated
Polymer to which the 4-propoxy cinnamoyl group was Introduced

[0116] The retardation film was prepared by using the same method as
Preparation Example 1, except that the ring-opened hydrogenated polymer
to which the 4-propoxy cinnamoyl group was introduced prepared in Example
4 was used instead of the polymer prepared in Example 1.

Comparative Example 1

[0117] The alignment film was prepared by using the same method as
Preparation Example 1, except that the compound of the following Formula
was used instead of the 5-norbornene-2-methyl-4-methoxy cinnamate
ring-opened hydrogenated polymer used in Preparation Example 1.

##STR00013##

Comparative Example 2

[0118] The alignment film was prepared by using the same method as
Preparation Example 1, except that the 5-norbornene-2-methyl-cinnamate
ring-opened hydrogenated polymer having no methoxy substituent of the
following Formula was used instead of the 5-norbornene-2-methyl-4-methoxy
cinnamate ring-opened hydrogenated polymer used in Preparation Example 1.

##STR00014##

Experimental Example 1

[0119] Photoreactive Property Evaluation--FT-IR Spectrum

[0120] In order to obtain the photoreactive property of the alignment
film, the FT-IR spectrum of each of the liquid crystal alignment films
that were obtained in Preparation Examples 1 to 3 was observed, and the
photoreactive properties were compared to each other based on the time
(t1/2) required until the intensity of the stretching mode of the
C═C bond of the Formulae 1a to 1c of the polymer during the exposure
(the mercury lamp having the intensity of 20 mW/cm2 was used) was
reduced by half and the energy value (E1/2=20 mW/m2,
t1/2). The results are described in the following Table 1.

From the comparison of t1/2 values, it could be seen that in the
case of Preparation Examples 1 to 3, the time was reduced by about 1/10
or more as compared to the case of Comparative Example 1 and thus the
liquid crystal alignment film according to the present invention had the
desirable photoreactive rate.

[0121] Evaluation of the alignment property (evaluation of the degree of
light leakage)

[0122] In order to evaluate the alignment property of the alignment film,
the liquid crystal retardation film that was prepared in Preparation
Example 1 and Comparative Example 2 was observed between two polarizers
that were perpendicular to each other by using a polarizing microscope,
and the transmittance thereof is shown in FIG. 1. That is, in order to
evaluate the transmittance, based on polyethylene terephthalate having a
thickness of 80 microns (trademark: SH71, prepared by SKC, Co., Ltd. in
Korea), the liquid crystal retardation film that was prepared in
Preparation Example 1 and Comparative Example 2 was provided between the
polarizers that were perpendicular to each other and the degree of
transmittance of incident light through the polarizing plate and the
retardation film was checked by using the polarizing microscope to
measure the degree of light leakage, which is shown in FIG. 1. As shown
in FIG. 1, in the retardation film of Preparation Example 1 according to
the present invention, the alignment direction of liquid crystal was
uniform regardless of the wavelength of incident light, but in the case
of when the alignment film of Comparative Example 2 was applied, it could
be seen that the alignment strength was reduced and the alignment
direction of liquid crystal was not uniform.

Preparation of the Photoactive Polymer Including the
Cycloolefin-Noncycloolefin Copolymer Compound

Example 5

Synthesis of the 5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene
copolymer

(1) Protection of 5-norbornene-2-methanol

[0123] 29.75 g of TiBAL (Triisobutyl aluminium, 0.15 mol) was put into the
batch reactor having the volume of 250 ml that was dried in the ice bath
while the agitation was performed, and 12.42 g of 5-norbornene-2-methanol
(0.1 mole) was slowly added thereto and the agitation was performed for
20 minutes.

(2) Synthesis of the protected copolymer of 5-norbornene-2-methanol and
ethylene

[0124] After the dried batch reactor having the volume of 250 ml was
prepared under an Ar atmosphere, 7.92 g of the protected
5-norbornene-2-methanol solution (30 mmol) and 50 ml of purified toluene
were added thereto. After the temperature of the reactor was increased to
70° C., 0.3 μmol of
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride used as
the catalyst and 1.2 mmol of MAO used as the cocatalyst were added
thereto, and the polymerization was performed for 20 minutes while the
pressure of ethylene was maintained at 75 psi. Next, ethylene was removed
under excessive pressure, and the reaction solution was dropped on a
large amount of methanol/hydrochloric acid aqueous solution (volume ratio
1/1) to obtain the polymer precipitate. The polymer that was obtained by
filtering the precipitate by using the glass funnel was dried in a vacuum
oven at 70° C. for 24 hours to obtain the
5-norbornene-2-methanol/ethylene copolymer (yield: 56.8%, Mw=74363,
PDI=1.73).

(3) The Modification of the Cycloolefin Copolymer

Synthesis of the 5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene
copolymer

[0125] The 5-norbornene-2-methanol/ethylene copolymer (18.4 g, 0.121 mol)
that was polymerized in (2), 4-methoxy cinnamic acid (Aldrich, 21.5 g,
0.121 mol), EDC [1-(3-dimethylaminopropyl)-3-ethylcarboimide
hydrochloride] (Aldrich, 37 g, 0.194 mol), and HOBT
(1-hydroxybenzotriazole hydrate) (Aldrich, 24.5 g, 0.182 mol) were put
into the 2-neck flask having the volume of 250 ml, and then dissolved in
100 ml of DMF. After the temperature was reduced to 0° C.,
triethylamine (Aldrich, 75 ml, 0.605 mol) was slowly dropped on the
reaction solution. After the temperature was increased to normal
temperature and maintained for 3 hours, when the reaction was finished,
the reaction solution was dropped on a large amount of methanol to
precipitate the polymer, and the polymer was filtered to obtain the
5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene copolymer to which
the 4-methoxy cinnamoyl functional group was introduced (yield: 90.5%).

[0126] 69.42 g of TiBAL (triisobutyl aluminium, 0.35 mol) was put into the
batch reactor that was dried in the ice bath and had the volume of 250
ml, 13.8 g of the 5-norbornene-2-carboxylic acid (Aldrich, 0.1 mole) was
slowly added thereto while the agitation was performed, and the
additional agitation was performed for 20 minutes.

(2) Synthesis of the protected copolymer of the 5-norbornene-2-carboxylic
acid and ethylene

[0127] After the dried batch reactor having the volume of 250 ml was
prepared under an Ar atmosphere, 8.35 g of the protected
5-norbornene-2-carboxylic acid solution (30 mmol) and 50 ml of purified
toluene were added thereto. After the temperature of the reactor was
increased to 70° C., 0.3 μmol of
isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride used as
the catalyst and 1.2 mmol of MAO used as the cocatalyst were added
thereto, and the polymerization was performed for 20 minutes while the
pressure of ethylene was maintained at 75 psi. Next, ethylene was removed
under excessive pressure, and the reaction solution was dropped on a
large amount of methanol/hydrochloric acid aqueous solution (volume ratio
1/1) to obtain the polymer precipitate. The polymer that was obtained by
filtering the precipitate by using the glass funnel was dried in a vacuum
oven at 70° C. for 24 hours to obtain the
5-norbornene-2-carboxylic acid/ethylene copolymer (yield: 22.7%,
Mw=65543, PDI=1.65).

[0128] The 5-norbornene-2-carboxylic acid/ethylene copolymer (13.2 g,
79.64 mmol) that was polymerized in (2), 4'-hydroxy-4-methoxy chalcone
(Aldrich, 18.4 g, 72.4 mmol), EDC (Aldrich, 22.2 g, 115.84 mmol), and
HOBT (Aldrich, 14.7 g, 108.6 mmol) were put into the 2-neck flask having
the volume of 250 ml, and then dissolved in 100 ml of DMF. After the
temperature was reduced to 0° C., triethylamine (Aldrich, 50 ml,
362 mmol) was slowly dropped on the reaction solution. After the
temperature was increased to normal temperature and maintained for 3
hours, when the reaction was finished, the reaction solution was dropped
on a large amount of methanol to precipitate the polymer, and the polymer
was filtered to obtain the 5-norbornene-2-(4'-hydroxy-4-methoxy
chalcone)ester/ethylene copolymer to which the 1-(3-methoxy
phenyl)-3-(2-hydroxyphenyl)-2-propenone functional group was introduced
(yield: 82.5%).

[0129] The 5-norbornene-2-carboxylic acid/ethylene copolymer (13.2 g,
79.64 mmol) that was polymerized in (2) of Example 6,7-hydroxy 6-methoxy
coumarine (Aldrich, 13.0 g, 72.4 mmol), EDC (Aldrich, 22.2 g, 115.84
mmol), and HOBT (Aldrich, 14.7 g, 108.6 mmol) were put into the 2-neck
flask having the volume of 250 ml, and then dissolved in 100 ml of DMF.
After the temperature was reduced to 0° C., triethylamine
(Aldrich, 50 ml, 362 mmol) was slowly dropped on the reaction solution.
After the temperature was increased to normal temperature and maintained
for 3 hours, when the reaction was finished, the reaction solution was
dropped on a large amount of methanol to precipitate the polymer, and the
polymer was filtered to obtain the 5-norbornene-2-(7-hydroxy 6-methoxy
coumarine) ester/ethylene copolymer to which the 7-hydroxy 6-methoxy
coumarine functional group was introduced (yield: 73%).

Example 8

Preparation of the Phenylnorbornene/Ethylene Copolymer to which the
Cinnamoyl Functional Group was Introduced

(1) Polymerization of the Cycloolefin Copolymer

Polymerization of the Copolymer of Phenyl NB and Ethylene

[0130] 5.1 g of phenylnorbornene (30 mmol) as the monomer and 50 ml of
toluene purified by the solvent were added to the dried batch reactor
having the volume of 250 ml. After the temperature of the reactor was
increased to 70° C., 0.3 μmol of
[PhCH(fluorenyl)(Cp)]ZrCl2 used as the catalyst and 1.2 mmol of MAO
were added thereto, and the polymerization was performed for 20 minutes
while the pressure of ethylene was maintained at 75 psi. Next, ethylene
was removed under excessive pressure, and the reaction solution was
dropped on a large amount of methanol/hydrochloric acid aqueous solution
(volume ratio 1/1) to obtain the polymer precipitate. The polymer that
was obtained by filtering the precipitate by using the glass funnel was
dried in a vacuum oven at 70° C. for 24 hours to obtain the
phenylnorbornene/ethylene copolymer (yield: 55%, Mw=89125, PDI=1.51).

(2) Synthesis of 4-methoxy cinnamoyl chloride

[0131] 53.5 g of the 4-methoxy cinnamic acid (Aldrich 0.3 mol)) and 124.9
g of SOCl2 (Thionyl Chloride, 1.05 mol) were put into the two-neck
flask having the volume of 250 ml, and then reacted with each other at
normal temperature for 24 hours. After the reaction was finished, the
distillation was performed to remove an excessive amount of SOCl2,
and the reactant was diluted with 100 ml of toluene and neutralized by
using the NaHCO3 solution. After the neutralization, the resulting
substance was dried by using anhydrous MgSO4, and filtered, and the
solvent was removed by using the rotary evaporator. Next, the substance
was passed through the silica gel to remove the impurity, thus obtaining
36.5 g of the white solid (yield: 62%).

(3) Friedel-Crafts Acylation reaction

Preparation of the Phenylnorbornene/Ethylene Copolymer to which the
Cinnamoyl Functional Group was Introduced

[0132] 19.8 g of the phenylnorbornene/ethylene copolymer (0.1 mol) that
was polymerized in (1), 29.4 g of 4-methoxy cinnamoyl chloride (0.15 mol)
that was synthesized in (2), and 150 ml of CH3CN used as the solvent
were added to the two-neck flask having the volume of 250 ml. 10 mol %
Cu(OTf)2 was added to the reaction solution as the catalyst, and the
reaction was performed at 80° C. for 8 hours. Next, the reaction
solution was dropped on a large amount of methanol to precipitate the
polymer, the polymer was filtered to obtain the phenylnorbornene/ethylene
copolymer to which the cinnamoyl functional group was introduced (yield:
87%).

Preparation Example 4

Preparation of the Alignment Film by using the
5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene copolymer polymer

[0133] The 5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene copolymer
polymer that was synthesized in Example 5 was dissolved in the
c-pentanone solvent in a concentration of 2% by weight, and applied on
the polyethylene terephthalate substrate (commercial name: SH71, prepared
by SKC Co., Ltd. in Korea) having the thickness of 80 micron by using the
roll coating process so that the thickness of the polyethylene
terephthalate substrate was 1000 Å after the drying. Next, the
substrate was heated in an oven at 80° C. for 3 minutes to remove
the solvent in the inside of the coating film and to form the coating
film. The exposing was performed by using a high pressure mercury lamp
having the intensity of 200 mW/cm2 as a light source while polarized
UV that was perpendicular to the proceeding direction of the film was
radiated on the coating film by using a Wire-grid polarizer prepared by
Moxtek, Co., Ltd. for 5 sec, so that the alignment was provided to form
the alignment film. Next, the solid in which 95.0% by weight of
cyanobiphenyl acrylate that was polymerizable by UV and 5.0% by weight of
Irgacure 907 (prepared by Ciba-Geigy, Co., Ltd. in Switzerland) as the
photoinitiator were mixed with each other was dissolved in toluene so
that the content of the liquid crystal was 25 parts by weight based on
100 parts by weight of the liquid crystal solution to prepare the
polymerizable reactive liquid crystal solution. The prepared liquid
crystal solution was applied on the photo-alignment film that was formed
by using a roll coating process so that the thickness of the film after
the drying was 1 μm, and the drying was performed at 80° C. for
2 minutes to align the molecules of the liquid crystal. The nonpolarized
UV was radiated on the aligned liquid crystal film by using a
high-pressure mercury lamp having the intensity of 200 mW/cm2 as a
light source to fix the alignment state of the liquid crystal, thereby
preparing the retardation film.

Preparation Example 5

Preparation of the Alignment Film by using the
5-norbornene-2-(4'-hydroxy-4-methoxy chalcone)ester/ethylene copolymer

[0134] The retardation film was prepared by using the same method as
Preparation Example 4, except that the polymer prepared in Example 6 was
used instead of the polymer prepared in Example 5.

[0135] The retardation film was prepared by using the same method as
Preparation Example 4, except that the polymer prepared in Example 7 was
used instead of the polymer prepared in Example 5.

Preparation Example 7

Phenylnorbornene/ethylene Copolymer to which the Cinnamoyl Functional
Group was Introduced

[0136] The retardation film was prepared by using the same method as
Preparation Example 4, except that the polymer prepared in Example 8 was
used instead of the polymer prepared in Example 5.

Comparative Example 3

[0137] The alignment film was prepared by using the same method as
Preparation Example 4, except that the compound of Comparative Example 1
was used.

Comparative Example 4

[0138] The alignment film was prepared by using the same method as
Preparation Example 4, except that the
5-norbornene-2-methyl-cinnamate/ethylene copolymer having no methoxy
substituent, which was represented by the following Formula, was used
instead of the 5-norbornene-2-methyl-(4-methoxy cinnamate)/ethylene
copolymer of Preparation Example 4.

##STR00015##

Experimental Example 3

[0139] Photoreactive Property Evaluation--FT-IR Spectrum

[0140] In order to obtain the photoreactive property of the alignment
film, the FT-IR spectrum of each of the liquid crystal alignment films
that were obtained in Preparation Examples 4 to 7 and Comparative Example
3 was observed, and the photoreactive properties were compared to each
other based on the time (t1/2) required until the intensity of the
stretching mode of the C═C bond of the Formulae 1a to 1c of the
polymer during the exposure (the mercury lamp having the intensity of 20
mW/cm2 was used) was reduced by half and the energy value
(E1/2=20 mW/cm2, t1/2). The results are described in the
following Table 2. From the comparison of t112 values, it could be
seen that in the case of Preparation Examples 4 to 7, the time was
reduced by about 1/10 to 1/4 as compared to the case of Comparative
Example 3 and thus the liquid crystal alignment film according to the
present invention had the desirable photoreactive rate.

[0141] In order to evaluate the alignment property of the alignment film,
the liquid crystal retardation film that was prepared in Preparation
Example 4 and Comparative Example 4 was observed between two polarizers
that were perpendicular to each other by using a polarizing microscope,
and the transmittance thereof is shown in FIG. 2. That is, in order to
evaluate the transmittance, based on polyethylene terephthalate having a
thickness of 80 microns (trademark: SH71, prepared by SKC, Co., Ltd. in
Korea), the liquid crystal retardation film that was prepared in
Preparation Example 4 and Comparative Example 4 was provided between the
polarizers that were perpendicular to each other and the degree of
transmittance of incident light through the polarizing plate and the
retardation film was checked by using the polarizing microscope to
measure the degree of light leakage, which is shown in FIG. 2. As shown
in FIG. 2, in the retardation film of Preparation Example 4 according to
the present invention, the alignment direction of liquid crystal was
uniform regardless of the wavelength of incident light, but in the case
of when the alignment film of Comparative Example 4 was applied, it could
be seen that the alignment strength was reduced and the alignment
direction of liquid crystal was not uniform, thus, the transmittance was
increased.